Method for removing impurities from mineral oils



July 23, 1946. c. H. M ROBERTS 2,404,405

METHOD" FOR REMO-VIN@ IMPUBITIES FROM MINERAL OILS Filed Deo. 16, 1959 7 23 I l/v w-:Nrok

CLA UD/us H M. ROBE/ers (l5 HARK/5, K/gcH, Fos Te/P HAR/Pls A rroR/VE Ys.

termed as wlflich.=term1.have reierenoel to impurities which Patented July 23, 1946 MErHoDroirREMoviNGIMPUm'rms mou/r1MINERAL" oil-ls L:(liand'ills Roberts, Palos Verdes Estates,

t, Calif., `assigne oPetrolite Corporation, Ltd.,

4 :Myi invention relatesytofthe purification Qi, ,oils and, mores-particularly, ,to ,al methodsnd apparatusoforremoving itvaterrdispersible @mpllties Vfrom -oi.l, :for examplefsremoving saline-material tlie process is l also applioablefto Marions y Qthr oils toremove impurities! capable` of .aheinig taken -uplbyetlemadditonof water. Y

It .is not uncommon Jto find oils foonft .initie ywaterpsolulb1 el ortwaterewettable l impurities and, most trequentlmethese ,vare-presentinftlieoil1in Y,

the form of, or associated-mth, y.Sina-l1 ;liqu id droplets )oresolidf iparticles dispersed orsemulsied throughoutftheeoil, thong-hn some instances tlieyrmaylbe in. solution j.in- -thefoil,;;asf in; theqease ofrvoertain-inorganic acids whichare soluble both in oil and .Water. Suchirnpurities `are@herein- Nvaterfdispersi-ole impurities, by

may -4 be ldispersedi in :wa-ter,- either ato produce .a

homogeneous isolution (as,- inflthe Ycase of Watersoluble Limpurities which aremiseible with or so'lulolel in, the i Awater and which, when 4dissolyed in Wa/ter, mayfsbe regarded asimolecularly -or ionfinally/:dispersed therein) forte produce-a Watercontinuous dispersion-including the impurity as theinternalf piiasei (as .in; the casefof Water-Wettable, Iwater'-insolublelimpurities) The removalof wateresoluble or` `water--iizettable impuritiesifromtsuoh boils 'isia problem which is -i'requently en countered; and-Which is 'grof particular importance in'j thef handling: oflp'etroleum'goils, crudeAv or topped, A containing salinel Jiriaterial,l such as dispersedisaltorgoileieldA bringand also in the removaloff reagentsiand reaetiontproduots in re- The dispersedpand frequently `very-i'loiglnly stabilize`d, condition ofthe impurities .makes -it ydifficult ,orf impossible tofaeoomplishthe desired purification by :ordinary nonileclal methods.

lAccording to the p-resentaprocess, 'suoli impurities are `removed-Joy forming/in; anovel manner, an artificial dispersionfor -emulsionfwhioh isV oilcontinuous ,and ,which includes dispersed Water droplets of different sizesor;l addedfunder `different conditions, this dispersion .being treated electrically to coalesce the water which, 'when separated, is found to contain most of the Waterdispersible impurities, and it is an object of the present invention to provide a-novel `method operating in:A this manner.

It is another object of the invention to,v introduce theadded water into the system Vata'plur'ality ofpoints, dispensing the Water lntothe oil in a manner Well suited 'to pro-duce anjemulsion 'A2 ordispersioncapable of, continuons electricite@- ment. By this mocl'e yof,neemt1.011,1it ,s/possible to Se@ureal desired.,heterogeneity zei-,partitie site I' @mentsfatldifierent sequential positions@ obtain the desired electricallyetreatakrleidispersien.

. lian,attemptismadeto addetneientireemount ,of water`r at .a Asingle povsitori,Lfollmvelxbyi @mixing step adapted to disper f the Wate into the oil, it will be found indnest that reaffinitely limitedrmiXing-faotion 4musi? be used; if g the process is to :be capable ofoontinuously vresolving the emulsion or dispersion intotoilzandewater,

-- without @the accumulation of such:` amount of sludgesaswould,interfere.iwithsthermaintenane lsiralolejnv,many?,instanoesto haven-presey.dispersion droplets 4 4 of ,added water a quite smallin L size, often'. eommensura Y with l thel dispersed limpuritns `which a; some- A-tiniespresente-in iaisize; of about: l, mu. Igfffthe en- Y tire amountu of iwater .ist added ;;at:y a .Asingleposi- "tionpitiis rs'ometimesffound' that an` ,electrically- :untreatable emulsionon dispersion: results if suffioieiitmixing action is)appliedftoiinsurethat some of the: added Water i is .dispersed in; .particles of such smalllsize. rlkewise, While/someV degree' of i lla'eterogeneityof L=partiole1size of -thezaddediwater can be obtained. by l an appropriate-singleemixing step, therange ofyparti'oleisizes isz'sonleti-rnes con- Asiderably lbelow` that Lwfiiiohz` is amostg-` desirable; yin -tb1e.pro`oess. .'Gnx some Voils-tine rangeof particle size@appears 'quite small iflsucli singlefstepmi-xingae'ltionisusednasiwilt remove the desiredproportionmof tlie' impurities.

L110W#through a t restricted ori'flc-ze, a lmore Jorl less heterogeneous partiel'eJsliZe distributionY may @be obtained; in Wilicrhl tlie-v particles varyfrorn; small to large LWli-th asing-le-predominant-size,ltl'ieiisize- Y- f requ en cy distrib-tion ollowing--the=wellknown Sion contains particles-showing two -resporiding-t the'adjustment-titte two dispersvresulting from previous refining steps. latter connection, the process can be used on with those of the impurities inthe oil in any def sired ratio to those of the larger sizes, thereby permitting great flexibility in adjustment of the treatability of the final dispersion, together with ability to obtain an increased degree of removal of the highly dispersed impurities; whereas, when using a single dispersing step, it may be'possible to secure enoughparticles of the desired small size only at the expense of'obtaining too lowv` a concentration of particles of the desired larger sizes, thereby leading to .difficultiesV in theV sub- K' sequent electrical resolution due to formation of sludge. Y,

It is an Vobject of the present invention to pro-V duce an electrically-treatable dispersion vrof desired heterogeneity as to the size of `dispersed water droplets therein.

It is another object ofthe present invention to add water to the system at two or more points separated by one or more mixing zones in which a controlled mixing action is applied. Another object of the present invention is to disperse a portion of the added Water into the oil in theform of relatively small droplets, and to disperse another portion of the added water into the oil at a later time, the later-added water being present in the form of droplets which are of anl average size larger than those produced inthe first dispersingfprocess.

-Further objects vand advantages of the inven, tion will be made evident hereinafterto those skilled-in the art. A The process is particularly adapted to the purification of oils prior to subsequent refining steps;

for example subjection to distillation or cracking temperatures. It is capable of taking out,

and particularly applicable to the removal of,

impurities which, upon heating. to refining or cracking temperatures, comprise lor form acids? or other materials-having a tendency to corrode f or form deposits in the subsequent refining equipv nient, or having a tendency to deleteriously affect the quality of the final products. Purification by the present process makes possible longz `trouble-free runs on such subsequent equipment,

and they process can well be operated to be maintainedon-stream with this subsequent rening equipment with no appreciable loss of oil.Y On

the other hand, the process is not limited to the f,

treatmentof oils preparatory to further refining.

The oil with which the presentinvention is concerned can be any oil having sucient resistivity to sustain an electric field at coalescing potential when this oil is present in Whole or in part as the continuous phase of an emulsion or dispersion in which the added Water is dispersed in accordance with theinvention. Petroleum oils Y are particularly well adapted for treatment by the process, whether in a crude state or Whether In the topped`oils or on various fractions obtained from oils.

Such oils can be dry, or substantially dry, or.

can contain dispersed water with which atleast some of the impurities may be associated, this Water being dispersed Vin the oil to form what is hereinafter. termed original Water droplets.

water' content, for example,` oils containing from 20%, to50% of Water (percentages here and elsewhere are by volume), and such oils are preferably first dehydrated to produce the starting material for the4 present purification process. The

preferred oils are those which contain no more 4 than a small amount of water, usually under about 8% and only very infrequently as high as 1015%. Best purification results are obtained by starting with an oil containing Ano more than a few per cent of water, for example, an oil containing from a fraction of 1% up to :5f8% ,and Ihavea decided preference for oils inthe-lower' portion of this range if a high percentage of the impurities is to be removed.

l Thewater which I disperse sequentially into the oilpreparatory to electric treatment should be relatively fresh, by which term I have reference to water capable of taking up, or becoming vvassociated with, the Water-dispersible impurities to be removed. This relatively fresh water need not be distilled Water and need not be entirely devoid of the impurities to be removed or other chemicals or minerals, and, in fact, the process is improved on certain oils by the presence of `small amounts of chemicals, as disclosed in certain copending applications, for example Nees, et al., Serial No. 312,745,5now Patent No. 2,380,458: It is imperative, however, that if the incoming yoil contains dispersed impurity-containing droplets, the added relatively-fresh Water should containthese impurities, Vif at all, in concentrationsY materially lower thanthe originally-present droplets, and if the oil' contains no such original drop lets, the `relatively fresh water should have a concentration, if any, in the impurities to be removed Which is very lovv.A

Y Ineieclgrthe process adds droplets of relative- Vly fresh water tothe Voil in controlled dispersing ning steps, if used. The necessity forvuseof a relatively fresh water. will be readily apparent from an example assuming the presence of 1% of brine in the incoming oil andthe presence of A1% of water in the oil resulting after separation of the coalesced water. If this incom- Y ing oil contained 100 pounds ofsalts per 1000 barrels of oil, these saltsbeing, for instance, pre- Y dominantly magnesium and calcium chloride, and

" if the added water is of the saine concentration .e Theprocess is not well adapted to oilsl of high in these impurities as are the original water droplets, then the separated oil will contain these salts in amount about 100 pounds per 1000 barrels, and the total reduction in the impurities willVV be negligible. -On the other hand, when operating with a relatively fresh water under the same circumstances, reductions in salt content of more than can be readily'obtained.

The electric field /utilized'in the process should be capable of bringing into combination or association the impurities and the droplets of relatively fresh water, and should, likewise, be capable of coalescing the water into masses of sulficient size to be readily separable from the oil.`

The eoalescing iields herein-used are usually of the high-Voltage alternating current type, though coalescing iieldsformed'by the use of directeurrent can, in some instancesybe substituted, though l the 'process is 'not concernedwith low-voltage fields exerting only a cataphoretic action',

The process can best bedescribed with reference to they treatment of mineral oils containing water-dispersibleV impurities, and the process hereinafter described will be exemplifiedA in this manner, without intention of limitation.

Likewise, appropriate apparatus willbe shown as exemplary, and inthe accompanying drawing:

Figure 1 illustrates diagrammatically one embodiment of the appara-tus capable of carrying out the process;V

Figure 2 is an enlarged view in vertical section of one type of mixing means useful in the process;

Figure 3 is an enlarged sectional View ofr a portion of the electrode structure shown in Figure 1;

and

Figure 4 is an enlarged sectional view of the distributing means shown'in theele'ctric treater of Figure 1. n y

Referring particularly to-Figure l1, the oil' to be treated may'be moved through pipe I El by a pump I I. If this oil is already of low water content, it can be discharged through pipe l2 and 'valve I3 into a tankv I4. If the water content ofthe oil is high, it is preferable first to dehydrate the oil'V by electricaLchemical, centrifugal, or other means, or merely by settling. This can be accomplished by opening a valve l5 so4 that theincoming `oil moves to a dehydrator l5 from which the excess water can be withdrawn through a pipe I1, and the oil of low water contentv through the pipeV |'8 for delivery to the tank I4.

The oil to be purified is withdrawn from the tank i4 through a pipe 20 by the action of a pump 2|, which usually supplies suflicient pressure to move the oil through the system while 'maintaining superatmospheric pressurev on the oi'l until' it discharges from the electric treater. If desired, the oil flowing in the pipe 20 may be heated by passagethrough a heat exchanger 22 and then flow along a pipe 23.

Any suitable means can be used for dispersing relatively fresh water into this oil in two or more positions, the dispersing steps being such as to facilitate the operation of the process, asv hereinbefore described. In the exemplary showing of Figure 1, the relatively fresh Water is added in two stages, and dispersion is effected by flow through mixing valves. For example, the first portion of the relatively fresh water may be supplied through a pipe 24 to a tank 2'5 and, from this tank, proportioned into the oil stream by use of a pump 25, moving the water through pipe 2l and valve 27a into the oil stream vin the pipe 23 at right angles at the junction 28.` If desired, this portion of the relatively fresh water can be through type and may well induce the desired mixing action by the turbulence attendant upon change in direction of flow or passage through a restricted orice. One readily-controllable type of mixing means is shown in Figures 1 and 2 as comprising a weight-loaded valve 3l providing a seat 32 in a partition 33. A valve member 3d is vertically movable toward and away from the v yseat 32 by use of an arm 36 pivoted at 31 to a post 38, and pivoted at 39 to a plunger 40 connected The' arm 36 carries an to the valve member,

yeo

adjustable weightY 4 l! so that. the'l mixing. action may be adjusted by moving the. weight. 41..

Thedispersion thusA formed. is shown asamoving along the pipe. 231 to. ajunctio'n. 44 under the ac.- tion ofI the pumps-21' andl 261, Hera, the second portion of relatively fresh water isv injected through a pipe 45' after'beingsuitably heated, if desired,'in a heatexchanger 4t.. This relatively fresh water is moved into the pipe 45= through a valve 45a therein by a pump 4l intaking from a secondtank 48. some instances, a simple injection of the second portion of water int-oi the oil streamv will mix the! two and give a .desired type of dispersioncontaining, for examplavsmall1` droplets of relatively fresh water as dispersed into the oil by the'rirst mixing or dispersing step, and larger droplets ofrel'atively fresh water dispersed into the stream by the injectingactionadjacent the junction 4'4". v However., in many instances, it is desirable to mix the constituents further and a mixing means 5Fl can be used inthis connection. This mixing means is shown as comprising a weight-loaded valve V5i similar to that previously described. The resulting dispersion is delivered to the electric treater but, if desired, can be additionally heated or cooled by use of a heat exchanger 53,

A valuable adjunct to the process and apparatus thus far described, and which can be used in place of or to supplement the dispersion of the i'lrst portion of the relatively fresh water inthe oil, is the addition of vsteam to assist in the formation of the desired dispersion. If steamv is moved into the pipe 23 in proportioned amount, this steam will be dispersed throughout the oil stream and will almost instantaneously condense: Depending upon the manner of injection of the steam, particles ofv relatively fresh water of different size can be thus dispersed, the relatively fresh Water in this instance comprising the condensate. Usually, such dispersed droplets formed by the injection of steam are quite small in size, and this is often desirable in the process.

As shown in Figure 1, steam from any suitable source may be moved through a pipe 5,1 and, upon opening of a valve 58, will be delivered to the pipe 23 through V.a pipe 59. Alternatively,'or at the same time, upon opening a Valve 60 the Steam may be delivered in lproportioned amount to the pipe 23 through a pipe 6I. Correspondingly, steam may be delivered either prior to or after dispersing the rst portion of relatively fresh water into the oil through the pipe 2. Often, such injection of steam can be used to eliminate the addition of relatively fresh lwater through the pipe 21, relying upon the later addition through the pipe 45 to supply the somewhat larger droplets of relatively fresh water which are desirably present in the dispersion undergoing electric treatment. Y l

While various electric treaters can be used in the process, Figures 1 and 3 show an embodiment which has been found to be very satisfactory and aration take place in the same tank. Such a tank is indicated by the numeral 10, and after operation for ,al period of time, containsr bodies of oil and water TI and 12, shown as separating at the surface or interface '13.

In view of the electrical system utilized, it is i desirable to maintain this surface or interfacer 1.3. at or about the position shown, and to accomplish this, therateof withdrawalof treated constituents from the tank may be. varied. The system shownincludes a water draw-oi pipe 14 equipped with apvalve 15.4 Extending upward from the pipe 14, and thuscommunicating with the water in the lower part of the tank 10, is a pipe 16, this pipe terminating at its upper end with the' body of Voil 1| and being provided at a4 position near the interfacial zone with a chamber 18.

An oil-water interface will thus form inthis chamber and any suitable means can'beused ,to control the withdrawal from the tank 10 to main.- tainV the interface 13 substantially constant in position. A float19 is shown in this connection and is mounted on apivoted arm 8 0, which is connected by link 8|, with a link 82 forming a part of the operating system for the valve 15. The float 19 is of such character as to sink inoil and float in water. Correspondingly, when the interface rises, the float moves upward and, through links 8| and 82, the valve 15 is opened -suiiiciently to increase the flow therethrough, thus tending This type of electrode structure presents a minimum impedance to gravitational separation .in the tank 10, the rings and supporting means therefor covering only a small fraction of the total cross-sectional area of the tank 10. Furthermore, the interstitial character of these electrodes'permits free ycommunication between the electric fields and facilitates rapid removal of coalesced water masses therefrom.

The incoming dispersion or emulsion is preferably delivered from the heat exchanger 53 through a, pipe I5 directly into the lower treatingspace 98. It is preferred .to move the dis- Y persionrradiauy outward in this neld so thatV it to lower the interface 13 until the float returns the valve 15 to its previousposition. The amount of treated oil moving from the upper portion of the tank 10 through a pipe 85 maylsi'milarly be varied by adjustment of a valve 86 therein'. y

This lpurified oil maybe moved to'subsequent refining equipment, either with orl without additional settling time, but is shown as discharging into a tank 81 from which any water separating from the oil can be withdrawn through a pipe 88, the oil being pumped from this tank to suitable refilling equipment for distillation, cracking, or other processing, if desired. The valves 15 and 86 act to maintain a; all times sufficient superatmospheric pressure in the tank v'|0'to prevent such vaporization of the lighter fractions of the oil as might interfere with satisfactory separa- The electrode system of this treater is disposed in an oil environment of sufficient resistivity as to permit maintenance of the electric eld under given operating conditions. In this connection, I prefer to use a live electrode structure suspended Y from insulators 89, and shown as including' an Theelectrodes 90, 9|, 94, and 95 are preferably of interstitial character, and the constructional details of the embodiment shown'will be clear by reference to Figures 1 and' 3. Referring to Figure 3, the electrode 90 may include'a plurality of concentric rings lll mounted on pins |0| secured to cross arms |02. Each ring provides ajlowerannular edge |04 adjacent which thel electric field is 'very concentrated. The electrode 94 is similarly formed, with a pluralityv of concentric'rings |05 terminating in upward-extending annular edges |09. By disaligningthe rings |00 and' |05, the most intense portion of any electric'eld established in the treating space 91 Will-be inclinedas indicated by the dotted lines |01. The electrodes 9| and 95 are similarly formedY and are preferably of smaller diameter than the electrodes 90fand 94.

viding upper and lowertreating spaces 91` and Y moves successively through vthe edge-to-edge elds and sets up desirable circulations intofthe treating space 98 from the zone thereabove and from the zone therebeneath, thereby Vpermitting recycling of some of the treated constituents through the electric field. Such radial discharge may be `effected through use of a distributor IIB, best shown in Figure 4 as including Va housing |1 attached to the pipe ||5 and provided withl a cap ||8 which may be permanently or adjustably spaced therefrom to provide an annular passage ||9 through which the dispersion is delivered to the lower treating space 98. A spring-loaded distributor can be used in this connection (of the typ shown in Figure 4) Vand can be made to exert a mixing action on the incoming constituents at the point of discharge into the eld, this beingoften desirable though not essential to the operation of the process. For example, the cap ||8 may carry a rod |20 slidable ina spider 2| and carrying a passaged spacer element |122. By disposing a compression spring |23 between the spider |2| and the spacer element |22, the cap ||8,'will be movedresiliently downward and will be displaced upward a distance determined by the rate of input of the dispersion.

Various means may be utilized for energizing the electrodes to establish suitable electric elds in the treating spaces 91 and 98. In the construction shown, all of the electrodes 90, 9|, 94, and 95 are maintained above ground potential, the only grounded portions adjacent the electrodes being the distributor HB, Ythe tank 10, and the body of water 12. By proper design of the electrical system, the potential between the intermediate electrode structure and the electrodes 90 and'9l can be made much higher than the p0- tential between any of the live electrodes and the grounded portions of the system. In Figure l, such a lsystem is shown as including lWO transformers |25 and |26 Yproviding secondary windings connected in additive relation. One terminal of each secondary winding is grounded as indicated by the numeral |21, and the remaining terminals are respectively connected to the inter- A across the upper treating space 91 will be V24,000

volts, as will also the potential across the lower treating space 98. However, the potential between the distributor ||6 and the electrodes 9| or 95 will be only 12,000 volts, as will be the eldinducing potential between thelower electrode 9| and the body of water 12, and which eld is often desirable in further treating the settling water Vmassesas Well as in sludge elimination. Use of such a system tends .to prevent short-circuiting to tliedistributor and .also Ypermits introduction of the dispersion directly .into afield ofhigh voltage. It will be apparent lthat by using different .electrode` spacings and/or different potentials, the voltage gradients in the. spaces 91 and 98 and the intensities of the treatingactions therein may be controlled as desired -to .produce the best treating effects on the oil being processed.

The preferred mode of operation is one in which the dispersing stepsare socontrolled as to produce a dispersion which .is continuously resolvable With the aid of an `electric field into oil and water, Without the accumulation of such amount of sludge -as Would yinterfere with the maintenancefof the electric field. This resolution can `be effected by coalescing treatment .in the electric field, aided, if desired, by .recycling through the electric field Vas mentioned above, followed by settling or other separating steps. If the dispersing steps are properly controlled, resolution into oil and water can be obtained, the Water being substantially free of oil, Within commercial tolerances, .but now containing the impurities extracted from the oil, either in their original or `somewhat modified state. Such a mode of operation Will prevent'the accumulation of suchamountof sludge, comprising unresolved emulsion, as would ,interfere with the maintenanceof the electric field.

If the incoming .oil contains .suspendedimpurities, these yare Aoften yof very small size.. It has been found desirable to have some of the relatively fresh Water .droplets of a commen- -surate oronly slightly larger size as this appears to `increase the total percentage reduction of impurities. If the relatively fresh water is added at a single point, vfollowed by -such mixing as will `produce particles-of this small, size, itis found onmany voils that sludge ,difficulties are encountered, as evidenced either by the inability to' maintain coalescing potentials across the electrodes .during continuous operation, or Iby the progressive accumulation of alayer of vsludge in the interfacial zone which -eventually may build up either to short-circuit the eelctrodes or to gradually pervade the bodies of -oil and Water, thus preventing the continuous Withdrawal from the treater of substantially oil-free Water and oil of suitably low Water content.

By the present invention, I can add a portion of the yrelatively fresh Water at one stage of the process and control the dispersing action topproduce such ,small droplets of relatively -fresh water, and can add another portion of the .relatively fresh Water at another stage of .the process and control the dispersing action to produce droplets of relatively fresh Water of an average size larger than those produced in therst stage. In this manner, I can control very definitely the proportion of small droplets and the proportion of larger droplets, and, if desired, can produce a dispersion containing Water droplets differing in size very materially and of a` homogeneity range considerably different and larger .than is possible in other processes. This has beenfound very desirable and conducive to `ahigher percentage ,removal of impurities, as well as making possible the continuous treatment of .Oils kat high throughput .rates with substantially complete vresolution While still obtaining the desired reduction in impurities.

.I prefer to `disperse the smaller droplets in the oil prior to the dispersion of the ,larger droplets -.in the `system sl'iovvn,y but the 4opposite sequence can Abe used WithoutA departing from the spirit of .the invention. The smaller ,droplets `can be 'formed either exclusively by the mixing means 30 ror by the injection of steam, as previously described, .or these actions can be used together. If steam is introduced through the pipe .59 .to supply the small droplets, the relaand, in most instances, itis desirable kto add the first portion immediately ahead of the Isecond portion. However, if desired, the -rst portion can be added to the oil a considerable time -prior to the addition ofthe laterjportion Without departing from the spirit of the invention.

One-Verydesirable mode of operation in purifying an oil containing dispersed impurities is'to avoid predominant combination of these dispersed impurities with the relatively -fresh :Water until the dispersion enters the electric eld. This insures that droplets of the relatively fresh Water "will be present in the dispersion to be acted upon by the field to bring them intoassociation or combination with the dispersed impurities.

'The amount of relatively fresh Water used in thevprocess Willvary with different voils and With the desired degree of purification. 'I'he Water content of the dispersion entering the'electric field should not be so high as 'to producefinvefrse phase emulsions of the oil-in-Water-type in such amount as cannot be handled by the electric eld. The vupper limit onmost oils appears to'be below 40% or 50%. Usually, the Water content of the dispersion 'is Aconsiderably Aless `and vmay commonly rangebetween 8% and 30%. Ifjthe incoming voil contains vrno Water, or contains'no more than 2% or 3% vof water, the total amount of relatively fresh water added Will usually be found within the range of 5% vto 20% 4to 'bring the total Water content of the dispersion to at least about 8%, and the most desirable percentage can be determined empirically. Likewise,the relative amounts of Water added at the different stages of the process will vary with' different oils andgno fixed Avalues can begiven. In some instances, the proportions added through the pipes 21 and 45 can be commensurate With each other but, in other instances, itwill be found desirable to introduce relatively less Water through the pipe 21 than through the pipe 45.

If mixing valves aroused to Vdisperse the relatively fresh Water into the oil, thepressure drops thereacross willvbe controlled to yproduce the desired type of dispersion, as outlined above.l No fixed values Vcan .be given in this -connection'fon Withsome oils, the total drop in pressure from 4the p ipe20 to the interior of the treater can be much larger than with .other oils. It Vcan be said, vhovvever, that the particle size of the relatively fresh Water decreases as the pressure drop vacross an emulsifying valve increases. Correspondingly, if the relatively fresh Water introduced through the pipe 2.1 is to form the desirable smalldroplets, the pressure drop lacross the mixing 'valve 3| will usually be greater than the pressure, drop across the subsequent valve -5l. It will be understood that the. desired mixing Yaction can be '.Ill-iY Lto yform the desired. dispersion.

obtained .without i-e.-io1d;ing .Y to adjustable V.Lor .weight-loaded valves, and suitable orifices,Y orjrestricted passages can be .substituted as y forming thegmixingor dispersing means. Likewise, the

valvefl', orequivalent restriction, may sometimesbe eliminated .andreliance vplacedupon turbulence. in the pipe H5 `or in the distributor Once the small.. droplets of relatively fresh water are dispersed in ,thev oil, they will-not beV materially disturbed by.a Vlater and relativelyflessV intense Ydispersing or mixing action. Y y

k:tIL'can be yusedto proportionthe( oil andvwater Vconstituents. The pressureY exerted by these pumps islpreferablyV suflicientrto force the d is-4 persion into the' treater and maintain a superatmospheric/pressure therein. Pressures Ain the treater tank 'HlV between Y10 and 50 lbs/sq.

orgabOVe, can be used but, in'most instances, a

pressure'in'this-tank of about 25flbs./sq. in. is. y

velectric iield is-preferably superatmospheriabut the most desirable temperature will vary with different oils.A -Ordinarily, temperatures .from 1009-1,V up to fthe 4boiling point of -wate'rr at the pressure existingrinthe tankV l0 can be used with ment at atmospherictemperatures. TheY heat can -befsupplied entirely by use of theheat ex. Y changer 53,-or'the Voil-and water constituents can be preheated Vbythe use of the heat exchangers 22,29, or 46.-.

4VThepreierredV mode of operation isV to` use Va process which is continuous throughout,for example, one-in which Vthe portionsY of` relatively -fresh water are added successively to al stream of Voil.^ However, semi-continuous or batch voperations are within the contemplation of the present invention.

Injsome Vinstances-it Vis desirable to the process to re-use a portion of the water separating in the electricrtreater, -re-combining this portion with a more -pure'water before dispersingit into `the success-and some oilsare susceptiblerto treat-V Y l lets of the relatively freshwater later added are Y oil.*Therelatively'fresh water resulting from suchY a combining step gives improved results` on 7 Y many-oilsr as evidenced by decreased sludging tendencies, lower cuts of the purified oil, and higher process efficiencyV invv general including a greater percentage removal of impurities.` While thereasons for these phenomena arenot com` pletely understood,Y it has been discovered thatV the eiiluent watercontains, asa result of the procs e'ss, desirable counter-emulsifying agents` extracted from the-oil, Ythese agents being of the type assisting inthe resolution ofV water-in-oil emul- If/such a mode of operation is desired, a portion Vof the'elliuent water can be moved through pipe |40. as *,controlled by valve vHH and delivered through-another valve I 42 to the pipe-2l. The

M0 4cancommunica-te with the intake ofth'e pump.26 .orrmaybe equippedwith a separate .-.pumptfor delivery of the effluent water tothe The relative settings of valves YZ'Ida'ndp l|42 or 12Y 45a and |45 will control the proportions of relativelyr fresh and eiiluent water, andthe best ratios can .be determined empirically. The resulting combined waterk should still be relatively fresh as mentioned above so as to be effective in removing impurities from the oil. y y Q When using steam toform the smallest dispersed droplets, the additional and supplementary relatively fresh water may often desirably be a combination of the water from the tanks25 or 48 and the eiiiuent water from the treater.y B'y blendingthe eiiluent water with the water` nwithdrawn from only one of these tanksyit is thus possible to secure a multi-compositionl system, and it is often desirable in this instance to have the smallest droplets formed by the condensing of steam, with droplets of next-larger average size comprising some of the eilluent water while the droplets of largest average size contain less or none of the ellluent water. Y

Even aside from the use of Asteam in the process, itis often desirable to have the droplets of smaller averagesize composed in part of eluent water and the droplets of larger average size composed of .the water in one of the tanks 25 or 48, usually the latter, though the invention is not in all instances limited to this mode .of operation. This appears to lead to improved treatability and excellent operation of the process in general.

Various changes and modifications can be made without departing from the Spirit ofY the invention as defined in the appended claims.

I claim as my invention:

1. A process for removing water-dispersible im-. t'

purities from a mineral.y oilfof low or negligible Water content, which process includes .the steps of: adding relatively fresh water to said oil and mixing the added water and the oil in aiirst mixing step to form an oil-continuous dispersion containing the relatively fresh water in the form of droplets; later adding more relatively fresh, Water to said dispersion and mixing the lateradded Water and said dispersion in a second mixing step to disperse the later-added relatively fresh water into the oil-continuous dispersion in 'the form of droplets 'in the oil, said mixing steps being controlled in such manner that the dropof an average size diierent from the droplets of the relatively fresh water rst added toV produce an emulsion containing'diierent-sized droplets of the water suspendedv in the oil; subjecting said emulsion to the action of an. electric lield of sulicientv intensity to coalesce the water to form coalesced masses comprising impurities from the oil; and separating the coalesced masses from the oil. v

2. A process for removing saline material from a mineral oil of low or negligible water content, said saline material being dispersed in the oil in the form of small saline particles, which process includes theV steps of rst emulsifying into said Voil small droplets of relativelyfresh water of a size commensurate with the dispersed saline particles; then emulsifying into the oil larger dropletsv of relatively fresh water to produce an oil-continuous emulsion containing `dispersed y coalesced 4Water and its' associated saline mate- `rial fromtheoil. l

3, A Continuous process for'removing waterdispersible impurities from a mineral oil of low or negligible water content, which process includes the steps of continuously mixing with a stream of said oil a proportioned amount of relatively fresh water to disperse same throughout the oil stream in the form of small droplets to form a stream of oil-continuous dispersion; later continuously adding to the stream of oilcontinuous dispersionanother proportioned amount of relatively fresh water and mixing this water with the oil-continuous dispersion to disperse this water into the oil of the dispersion in the form of droplets having an average size larger than said small droplets iirst dispersed into the oil to form a stream of a resulting electrically-treatable oil-continuous dispersion capable of being continuously resolved with the aid of a coalescing electric field into oil and water without the accumulation of such amount of sludge as would interfere with the maintenance of said electric field; and continuously subjecting said stream of said resulting dispersion to the action of such a coalescing electric eld to coalesce the water into masses of sufiicient size to settle from the oil and collect as a body of water below said electric field.

4. A process for removing water-dispersible impurities from a mineral oil of low or negligible 14 water content, which process includes the steps of: first adding to the oil and mixing therewith in a first mixing step a -iirst portion of relatively fresh water to disperse the relatively fresh water into the oil as droplets of heterogeneous particle size with an intermediate particle size predominating in number; then adding to this dispersion and mixing therewith in a second mixing step a second portion of relatively fresh Water to disperse the water' thus added into the oil as droplets of heterogeneous particle size with an intermediate particle size predominating in number, the intermediate particle size produced by said rst mixing step being smaller than the intermediate particle size produced by said second mixing step and the range of particle size between the smallest droplets produced by the rst mixing step and the largest droplets produced by the second mixing step being greater than the range of particle size produced by either of said mixing steps individually; subjecting the resulting oil-continuous' dispersion to the action of a coalescing electric field to coalesce the dispersed droplets thereof into masses comprising said impurities and of a size to settle from the oil; and gravitationally separating said masses from the oil.

CLAUDIUS H. M. ROBERTS. 

